Detergent compositions



3,024,197 Patented Mar. 6, 1952 3,024,197 DETERGENT COMPOSITIONS ManfredDohr, Dusseldorf-Werster, Carl Wullf, Dusseldorf-Benrath, and BrunoWerdelmann, Ratingen, near Dusseldorf, Germany, assignors to Henlrel 81Cie. G.m.b.H., Dusseidorf-Holthausen, Germany, a corporation of GermanyNo Drawing. Filed Dec. 10, 1957, Ser. No. 701,702 Claims priority,application Germany Dec. 11, 1956 13 Claims. (Cl. 252117) This inventionrelates to improved detergents.

It is known that the properties of certain surface-active agents whichare used as detergents or detergent components can be improved by theaddition of fatty acid amides and in particular fatty acid alkylolamides. The fatty acid amides and particularly the fatty acid alkylolamides have, however, the disadvantageous property of swelling in water,so that detergents prepared from the same have a certain sensitivity towater which is disagreeable, particularly when the surface-active agentsthemselves already exhibit certain hygroscopic properties and do nothave suflicient mechanical strength, particularly when wet or moist.

One object of this invention is to overcome the above mentioneddisadvantages.

A further object of this invention is a detergent of superior mechanicalstrength and properties in shaped form, as for example in the form ofbars or pieces.

A still further object of this invention is a synthetic detergent whichmay be utilized in bar or piece form as a personal soap with excellentmechanical properties and compatibility for the skin.

A further object of this invention is a detergent with excellentmechanical strength.

These and still further objects will become apparent from the followingdescription.

In accordance with the invention it has been found that the propertiesof conventional detergents may be improved in many respects, as forexample with respect to mechanical strength, water-resistance,compatibility to the skin and the like by the addition of boric acidesters of fatty acid alkylol amides.

.The borates of fatty acid alkylol amides to be employed in accordancewith the invention are obtained in a simple manner by heating acids ofboron or their anhydrides with the fatty acid alkylol amides andpossibly removing the water produced thereby in known manner, as can bedone for example by the passage therethrough of inert gases or with theuse of boiling inert solvents. By anhydrides of boric acid, there areunderstood here all compounds which contain less bound water ofconstitution than boric acid of the formula H BO so that as anhydn'de ofboric acid there can be used for instance metaboric acid having theformula HBO tetra-boric acid having the formula H B O or boric anhydridehaving the formula B In accordance with the invention there can also beemployed mixed anhydrides to which a uniform chemical composition cannotbe ascribed. There is preferably employed boric acid of the formula H 30which is melted together with the alcoholic esterification component attemperatures of 80 to 160 C. At this temperature, the Water of reactionproduced escapes and the substantially anhydrous esters are obtained.The boric acid esters which are to be used in accordance with theinvention can however also be prepared by transesterificationinterchange of ester radicals) of esters of boric acids withcorresponding fatty acid alkylol amides.

The fatty acid alkylol amides from which the boric acid esters to beemployed in accordance with the invention are derived, can contain 8 to30 and preferably 10 to 20 carbon atoms in the fatty acid radical. Theremay be concerned in this connection saturated or unsaturated fatty acidsof natural or synthetic origin, preference however being given toalkylol amides of straight-chain fatty acids. The one valence of thenitrogen atoms of the fatty acid alkylol amides is replaced by analkylol radical which may contain up to 5 carbon atoms. The othervalence can be bound by a hydrogen atom, an alkyl radical or an alkylolradical, in which connection the alkyl or alkylol radical can alsocontain up to 5 carbon atoms. There are preferably employed boric acidesters of fatty acid alkylol amides which are derived from mono- 01'diethanol amines or from monoor dipropanol amines and particularly fromthe corresponding iso-propanol amines.

In the preparation of the substances which are to be used in accordancewith the invention, boric acids or boric acid esters and fatty acidalkylol amides are to be used in such quantity ratios that l to 3 andpreferably 2 to 3 molecules of fatty acid alkylol amide are present foreach atom or boron. Accordingly, the esters to be employed can beincompletely esterfied, i.e., free hydroxy] groups can be contained inan ester molecule as well as a boric acid radical, or, if fatty acidalkylol amides having more than one hydroxy group in the amide radicalare used, also in the amide radical. However, the completely esterifiedproducts, i.e., those which do not contain free hydroxyl groups eitherin the boric acid radical or in the amide radical are of particularpractical importance.

In accordance with the invention, however, there may also be employedfatty acid alkylol amide boric acid esters which contain radicals ofother alcohols bound in ester form. In this connection, there may beconcerned radicals of lower aliphatic, cycloaliphatic or aromaticalcohols, i.e. radicals of alcohols having 1 to 8 carbon atoms in themolecule. Of particular interest, however, are alkylol amide/alcoholmixed esters which contain radicals of higher alcohols, particularlyradicals of fatty alcohols, in the molecule, i.e., radicals of aliphaticalcohols having 8 to 30 and preferably 10 to 20 carbon atoms in themolecule. When using the fatty acid alkylol amide/fatty alcohol mixedesters, the molar ratio of fatty acid alkylol amide to fatty alcohol isin general not less than 20:80 and preferably greater than 50:50, forinstance 60:40, :30, 80.20, etc.

These boric acid esters are water-insoluble substances which do notswell in water and have a frequently waxlike consistency. Their meltingpoint frequently rises and falls, particularly as compared withhomologous series, with the melting point of the organic componentcontained therein. Boric acid esters of fatty acid ethanolamides whichare derived from straight chain saturated fatty acids having 10 to 20carbon atom have melting points within the range of to C. These areproducts of preferred use. Boric acid esters of unsaturated and/orbranched-chain fatty acid alkylol amides or mixed esters with fattyalcohols have lower melting points. For the preparation of solidproducts, such as shaped cleaning agents, bar soaps or else powered,flaked and similar washing agents, it is advisable to use boric acidesters having melting points of at least 40 C. and preferably 50 C. andhigher. For the preparation of liquid or paste preparations, such asliquid or paste preparations serving for shampooing or shaving, boricacid esters of lower melting points can however also be employed.

The quantity of boric acid esters to be added depends on the nature ofthe surface-active substances and the effect desired. In general thereneed not be employed a larger addition of boric acid ester than thequantity of surface-active substance present, the quantity ofsurfaceactive substance referring to the active substance free fromfillers or diluents, One preferably operates, however, with smallerquantities, for instance quantities less than about 50% by weight.Frequently even much smaller quantities, for instance quantities of 2 to15% by weight, are sufficient to obtain a satisfactory result, and in afew cases a good elfect can still be noted with quantities of the orderof 1% by weight. These quantities refer to the quantities ofsurface-active substance=l% by weight.

In accordance with the invention both anionic and nonionicsurface-active substances can be combined with the fatty acid alkylolamide/boric acid esters. These materials include both soaps and thelarge group of anionic synthetic surface-active substances, includingthose which are only partially affected by hard water and those whichare unaffected by hard water and included under the name syndet, whichas water-solubilizing group contain preferably sulfonic acid group orsulfuric acid semiester groups, in which connection these group may alsobe neutralized. The soaps to be combined with the boric acid esters canbe derived from fatty acids of natural or synthetic origin, in whichconnection in the case of the fatty acids of natural origin, there canalso be concerned hardened or OtherWiSe processed fatty acids of naturalorigin, particularly fractions of natural fatty acid mixtures. Among thefatty acids of synthetic origin, there may be mentioned by way ofexample those which are obtained by the oxidation of synthetic alcohols,for instance those obtained from the addition of carbon monoxide andhydrogen to olefines (oxosynthesis), or those obtained from thecarbon-monoxide hydrogenation (synolsynthesis). As further anionic,surface-active substances, mention may be made of the ether carboxylicacids, which can be prepared from high-molecular aliphatic orcycloaliphatic alcohols by reaction with the corresponding halogencarboxylic acids, particularly with chloracetic acid, in the presence ofacid-binding agents, or the derivatives of amino acids or proteinhydrolysates which contain fatty acid radicals bound in amide form andcan be prepared by known methods.

The preparations in accordance with the invention are, however, usedwith particular advantage, together with the syndets. Depending on thewater-solubilizing radical present, this group of surface-activesubstances can be divided into sulfonates, which are salts of truesulfonic acids, and into sulfates, i.e., those substances which arederived from sulphuric acid esters. Within the group of sulfonates,there may be mentioned by Way of example the alkyl or cycloalkylsulfonates which are obtained from aliphatic or cycloaliphatichydrocarbons by treating the hydrocarbons by radiation with actiniclight or by reaction of catalysts With mixtures of sulfur dioxide andchlorine or of sulfur dioxide and oxygen and converting the productsproduced in this way into the corresponding sulfonates in the knownmanner by treatment with caustic alkali, of the various types ofalkyl-aryl sulfonates which have gained particular importance, mentionshould be made in particular of the alkyl or cycloalkyl benzenesulfonates in addition to the alkyl or cycloalkyl naphthalenesulfonates. Alkyl benzene sulfonates which are prepared from thetetrapropylene obtained by the polymerization of propylene have gainedparticularly wide acceptance. As further representative of the sulfonatetype, there may be mentioned the fatty acid esters of oxalkylsulfonicacids or the fatty acid amides of amino alkyl sulfonic acids in whichthe alkyl groups of the sulfonic acid radicals contain 2 to 4, andpreferably 2or 3 carbon atoms.

Among the group of anion-active substances of the sulfate type, thefatty alcohol sulfates should be particularly mentioned, the fattyalcohols from which the fatty alcohol sulfates come can be of naturalorigin, i.e., they may have been obtained from natural products whichcontain fatty alcohols, for instance in the form of esters, as forexample from whale oil or beeswax, by saponification of these esters.The fatty alcohols can, however, also have been obtained from fattyacids of naturalior synthetic origin by reduction. Finally the fattyalcohols from which the corresponding sulfates are prepared may beobtained completely synthetically, for instance by carbon monoxidehydrogenation or by the addition of carbon monoxide and hydrogen toolefines followed by the reduction of the aldehydes which are thusformed. In addition to these sulfates, however, there should also bementioned the sulfates of fatty acid partial esters or fatty acidpartial ethers of multivalent alcohols. They include for instance thesulfated glycol or polyglycol esters of fatty acids, the sulfated fattyacid monoglycerides, sulfated fatty alcohol polyglycol others or fattyalcohol polyglycerin ethers, etc. Finally, in this connection thereshould also be mentioned the sulfation products of fatty acid amides orfatty acid esters of alkylol amides, and particularly of ethanol amides.

Insofar as mention has been made of fatty acid or fatty alcoholderivatives in the above enumeration of alkyl or cycloalkyl radicals andcorresponding hydrocarbons, there are meant thereby those which contain8 to 24 and preferably 10 to 18 aliphatic or cycloaliphatic carbonatoms.

The Washing and cleaning agents in accordance with the invention canconsist, aside from the boric acid esters added, substantially only ofsurface active substances, but they may also contain in additionordinary detergent additions.

The invention makes it possible to prepare detergents which consistessentially of the surface active substance in the same way as wasgenerally possible heretofore, only in the case of soaps. Suchdetergents can therefore be brought into the form of pieces, shavings,chips, strings, flakes, etc., by the use of the machines customary inthe soap industry, such as soap mills, extrusion presses, bar cuttersand striking presses. The addition in accordance with the invention ofboric esters of fatty acid alkylol amides and boric acid mixed esters offatty alkylol amides and fatty alcohols therefore imparts to thepreparations prepared therewith processing properties such as in generalare found only in the case of pure soap products. The preparations inaccordance with the invention possess high mechanical strength in usewhich is revealed in particular in high resistance to rubbing off and toresistance against water. If bar-shaped detergents having thiscomposition and prepared on basis of synthetic surface-active substancesbecome moist, they will of course take up water, but they will give itofl again upon drying without the formation of swollen parts which areeasily rubbed off and no longer give off the water being formed on thesurface.

The invention, however, cain also be employed in the case of the knownloose detergents, particularly the powdered or granulated detergents andthe paste detergents, which may then also contain the additionsubstances customarily employed. These addition substances include forinstance dior tri-alkali orthophosphates, mono-or dialkali carbonatesand other salts of alkaline reaction, sodium sulfate, magnesium sulfateor other neutral slats, meta-, pyroor polyphosphates, particular mentionbeing made in connection with the latter of the compounds Na P O and NaP O Furthermore, oxygen-liberating substances can be present,particularly perboratese or similar substances. Finally addition substances which are customarily employed such as cellulose glycolates orother water soluble cellulose derivatives, optical brighteners, dyes,etc., can be present in the powdered or paste detegrents of theinvention. In the case of loose detergents, the boric acid esters to beused in accordance with the invention have proven to be excellentperfume-carriers.

The incorporation of the boric acid esters to be used in accordance withthe invention in the detergents can be effected by the most variedmethods. If the anionactive substances or the detergents or detergentcom-- ponents" produced therefrom are in solid, loose form,

for instance in powder form, the loose boric acid esters can first ofall be mixed with them or the molten boric acid esters or boric acidesters dissolved in organic solvents can be sprayed onto the finelydivided detergents, the powdered detergent being preferably moved about,for instance in mixing drums, or by screws, agitating arms, etc., andpreferably by transforming the powdered detergent into a fluidizedlayer. These powdered detergents can then be further processed to formfor instance fine soaps or bar soaps, etc. However, it is also possibleto start with a highly concentrated paste batch of the anion-activesubstances and mix it, preferably in warmed state, with the molten boricacid ester. It is advisable to use for this purpose pastes which containless than 50% Water and preferably less than water. The mixing can bedone in known devices, such as agitators, kneaders, screw presses andsimilar apparatus. The mixtures obtained in this manner can now eitherbe further processed into bar soaps, or they can be atomized and broughtinto contact with other detergent components.

The great advantage of the boric acid esters of fatty acid alkylolamides and their mixed esters with fatty alcohols resides in the factthat the boric acid esters do not swell in water. Accordingly, upontheir incorporation in detergents, it is not only possible to avoid anincrease of any sensitivity to water which might possibly be present,but in addition, water-sensitive, anion-active substances become lesssensitive to water.

If synthetic anionic surface-active substances or soaps prepared fromsynthetic fatty acids are worked into cake soap, considerabl difilculties occur on the machines customarily employed for this purpose,such as the sticking and smearing of the mass on the milling rolls andthe uncut bars formed have a rough nature and non-homogeneous structureand tear apart upon pressing. The cakes obtained, have a dull surfaceand great sensitivity to water, which makes itself noticeable in themanner that the parts of a piece of soap which come into contact withwater swell and are easily rubbed off during the washing, so that alarge amount is used and wasted. By the addition of the boric acidesters in accordance with the invention, there are obtained, however,cakes of excellent mechanical strength, particularly when the boric acidesters to be employed have a melting point above 50 C. and preferably amelting point above 65 C.

The boric acid esters to be used in accordance with the invention impartan excellent compatibility for the skin to the detergents. Accordingly,the boric acid esters are suitable in particular as additions fordetergents which are intended for use on the skin or which upon usenecessarily come into contact with the skin.

Upon the preparation of detergents, such as cakeshaped detergents thepredominant component of which consists of active substance, at largenumber of fillers and superfatting agents were previously employed.These fillers and super-fatting agents can of course also beincorporated in the detergents of the invention, particularly when thesedetergents consist predominantly of anion-active substance. The boricacid esters to be used in accordance with the invention are directlycompatible with such fillers and supe'r-fatting agents. Such substancesinclude for instance waxes, fatty acids, fatty alcohols, fatty acidesters, particularly fatty acid glyceridesincluding fatty acid partialglycerideslanolin, lecithin, cellulose derivatives etc., and cantherefore be incorporated directly together with such substances in thedetergents. However, the fillers or other substances customarily presentin detergents, particularly when they are produced as cakes, such asperfume, titanium dioxide, bentonite, kaolin, colloidal silica, boricacid, urea and other compounds can also be used. There can furthermorebe incorporated additions which serve for the obtaining of specialcosmetic or pharmaceutical effects, such as skin protection agents,deodorants, disinfectants, and other medicamental additions.

6 The following examples are given by way of illustration and notlimitation.

Example 1 In a mixer customary in the soap industry (crutcher) thefollowing components are mixed together at about 50 C.:

60 kg. of a pasty fatty alcohol sulfate (sodium salt of the sulfuricsemi-ester of saturated fatty alcohols having 12 to 18 carbon atoms),which contains 10% by weight water and at most 6% by weight inorganicsalts (essentially Na SO and/ or NaCl),

12 kg. of the ester of from 3 mols of coconut fatty acidmonoethanolamide and 1 mol of boric acid (clear melting point=98 C.),

6 kg. of a mixture of approximately equal parts of palmityl alcohol andstearyl alcohol,

15 kg. paraffin of a melting point of 50 to 52 C.,

12 kg. carboxylmethylcellulose,

1 kg. perfume Though the mixing of the components can be effected in anydesired sequence, it is advisable to first mix the fatty alcohol sulfatepaste together with the Other components except the boric acid ester, ata slightly elevated temperature, for instance at about 50 C., and to addthe molten boric acid ester to the mixture at this temperature.Afterthorough working of the mass, it is milled three times in thecustomary manner. The shaving obtained are formed into an endless barwhile still warm in a vacuum double-bar press, this bar then beingconverted into cakes in the known manner.

The cakes obtained are equal in appearance to the best toilet soap. inuse they give a fine bubble foam. The tendency which is always presentin the case of the known cake cleaning agents having a base of syntheticWashactive substances to take up water during use and thereby soften hasbecome as low as in the case of conventional cake soaps by the additionof fatty acid ethanolamide boric acid esters. The water which has beenabsorbed is given up again immediately without the cake thereby beingsoftened permanently.

Example 2 The following substances are melted together in a steam-heatedboiler:

10 kg. alkylbenzenesulfonate (Na-salt, alkyl chain substantially C 40kg. sodium l-alkylsulfonate (obtained by reacting coconut fatty alcoholsulfate with Na SO The alkylbenzenesulfonate and the alkylsulfonate eachcontain about 5% by weight H 0 and about 7% by Weight inorganic salts(substantially Na SO Into the liquid mixture, there is now added whilestirring vigorously 10 kg. of an ester of 3 mols coconut fatty acidmonoethanolamide and 1 mol boric acid 25 kg. stearine 10 kg. of amixture of approximately equal parts of palmityl alcohol and stearylalcohol 5 kg. polyethylene glycol (molecular weight=6000) The mixturewhich is still liquid at about C. is introduced into a plate-coolingmachine. After standing for 24 hours, the curd-soap-like blocks areremoved from the plate-cooling machine, cut and stamped in the knownmanner. There are obtained cakes of good foaming property and highcleaning power. Despite the alkyl benzene sulfonate content, no damageor irritation to the skin is produced upon use.

Example 3 Cake cleaning agents of the following composition wereprepared by the method described in Example 1:

40% by weight coconut fatty acid monoglyceride sulfate (sodium salt) I15% by weight alkylhenzenesulfonate (sodium salt,alky1 I 1.0% by ht ofan ester 3 mol stearylmonoethanol- 15 i rannerfor the preparation offine soaps, .t'he're are added, I I 1 I 1 r I j :ferrcd to, the entiresoap batch,- a molten mixture of I imonoethanoiaml-d I I by :weight,perfume and 4% by weight of. an ester tures indicatedin the-table.Thereupon' foam waspm- I i duced at these temperatures inan apparatusconstructed according to J'. Ross and G. D, Miles; Oil and Soap, I I

vol. 18, pages 99 tov 102 (1941), and the height of the foam read afterstanding for 0,, 1 3,5 and minutes. Thereupon the heights of the foamswereread after the said periods of time with a given bath liquor andthese; I

ch'ain' about C )I I I I I I I I 14% by weight stcaric'acid I I I I I Ii I I 4% by weight polyethylene glycol (molecular :we1ght= I 5 5% byweight of apolyether having the, overall general 1 I a I formula I Y II, f i values were placed 'as foam' values in the'table; The j IHOP--(C2H4O)a+(C3H6O)b-F(C2H4O)j I v I action ofthe additions is morefavorable the higher the I I t an r g molecularwfiight 3 a 1 10,indicated foam values. In order to compensate for ex- I I I I ing rangof about'5t) to.55 C., themo r t i perimentali errors by, differentamounts of dirtin the i I Of the P the, molecule: indicated by th l h lq ors, the values contained in the table Werecal 3 pa s being i n' trange of 1500 TO 1800? culalted as average values of a series ofmeasurements 7 (Commercial. product Pluronic F 68.) I I I amide and 1mole boric-acid Foam Values 1% by weight perfume I I O DeItergmt 1 y ih: titanium dioxide I W tltlti WWW: was

3% by weight 3,3,5,5',6,6'-h,exachlor-2,2'-dioxydiphenyl- :lcitl etlmacid ester methane 2O nolumule 5% by weight water I III I I I I I 6 2%by weight inorganic. salts, essentially N32SO4 1M I I I if It isadvisable in the preparation to dissolve the halo- 34 I 41 I 47genphenol in the molten boric acidester and add the re- I I I p I Inaining components to the mixture in this form. There i obmmed Cakeswhich do 99h a h We I I ,If: the ester of 3 mols coconut'fattyacid'monoethanol- I I 'hlchhave long'lastmg deodonzmg actwn i v:amide and 1 molboricacid is replaced by the same 5quan- Example 4 itity by Weight of the ester from 2 mols coconut fa tty I I p n acidmonoethanolamide and 1 inol of bIo'r ic' acid or by I To customary Soapbatch" Such as used m known I the ame quantity by eight ofZ-molscoconutfatjty acid v a I e, l 11101 coconut alcohol and 3 mols i b ricacid, similar results are obtained I E 3 mols coconut fatty acidmonoethanolamide and l 3 Example 6 lol boric acid. The soa batch is thenthoroughly 5 I I I orlted, milled in known r anner' and worked into an Ii Equal Part? by 8 9 l l ,bqne' q f p I v I i ldless bar on an eXtrusionpress, I By c'utting and stamp" I i I nut fatty and 'f i j iw m de(mating, =9. I II I g, vthere areobtained cakes of toilet soapp Theb'or'ic i the addltmn Product 9f 9731015 0f e h l n 0x155 ap ifoam avery finely-porous creamy structure.

Example 5 By the hot-spraying of a paste detergent batch and addgeneousmixture. This mixture, which melts approximately in the region of to C.is cast in molds into bars of a diameter of about 2 cm. The shapedarticles produced in this manner are excellently suitable for perboratein known manner, there was prepared a 45 the removal of spots,particularly grease spots, from tshing agent of the followingcomposition:

% by weight sodium alkyl benzene sulfonate (alkyl chain about C textileswhich consist of synthetic polyamide fibers (nylon or perlon). For thispurpose the spotted places are rubbed vigorously with the bar and thenwashed thoroughly with Warm Water.

melted together to form. a bomol I ::id,ester in thcse'cakes acts asaniexjcellent fixing'agent 1 I to m of ya'yfalty C hOI pr p red byeduction of coco- I I I Ir the perfume and furthermore .upon use impartthe 40 nut fatty fields a y Weight coconut fatty alcohol Sulfate (Sodium5 Instead of the fatty alcohol polyglycol ether described,

salt) other non-ionic surface-active substances can be employed '7 byweight Na- O.3.3SiO in the same manner, particularly if they are presentin by weight NaBO .H O .3H O the form of oily or pasty substances at thecustomary 1 y Weight Mgsios storage temperatures of 10 to 40 C. Suchsubstances Y y Weigh! carboxylmethylceuulose 5 includealkylphenolpolyglycol ethers, fatty acid polyglycol y Weight 2 4 estersand polyglycol ethers which are derived from parby weight Water tialethers of fatty alcohols with polyvalent and particu- 70 by weight Na PO- or NaslsOm larly 3-6-valent alcohols or from partial esters of fatty7 k sample of this detergent was treated with 25% by acids with the saidpolyvalent alcohols. The non-ionic ght coconut f tt acidmonoethanolamide, While compounds which can be employed in accordancewith if sample was treated with by weight of an the inventionaccordingly contain in the molecule as hyfrom 3 mols coconut fatty acidmonoethanolamide drophobrc component aliphatic hydrocarbon radicalshavone mol of boric acid For this purpose the mg 8 to 24 and preferably10 to 18 carbon atoms and as l cats to be added were dissolved in about10 times hydrophilic Component 4 t0 4, n preferably 6 to 16 r quantityof ethyl alcohol and sprayed onto the powglycol ether Tadlcals- 1ddetergent which was kept in motion. Dirty launwas washed with thesesamples and a further unted sample of detergent in agitator-blademachines, a bath ratio of 1:15 in water of 18 German lness.

1e Wash was introduced into the freshly prepared 5, which was heated sothat after 35 minutes the rig point was reached. After an additional 15minof heating while boiling, samples of the bath liquor taken. Thesesamples were cooled tothe tempera- 75 Example 7 For the preparation of abath addition 25 kg. pine needle oil (terpene free) 20 kg. isopropylalcohol 50 kg. of an aqueous fatty alcohol sulfate solution, whichcontains about 35% by weight of the ammonium salt of a sulfuric acidsemi-ester of saturated fatty alcohols having l2 to 18 carbon atoms, andnot more'than 5% by weight inorganic salts are mixed while heating to 50there is slowly introduced kg. of a molten ester of 3 mols coconut fattyacid monoethanolamide and 3 mols boric acid (clear melting point=98 C.)

Example 8 For the preparation of a cream hair-wash 90 kg. of a pastefatty alcohol sulfate (sodium salt of the sulfuric acid semi-ester ofsaturated fatty alcohols having 12 to 18 carbon atoms) which contains byweight water and at most 6% by weight inorganic salts (essentially Na Soand/ or 'NaCl) are mixed with heating to 50 C. There are then slowlyadded while stirring 6 kg. of the molten ester of boric acid and fattyacid ethanolamide described in Example 7 C. Into this mixture,

and the mass is stirred until cool. There are then added 4 kg. liquidegg yolk of technical grade whereupon perfuming and coloring areeffected as desired. There is obtained a cream hair-wash of excellentfoaming power. By the addition of the boric acid ester, the foam becomescreamier, denser and firmer. The degreasing action of the fatty alcoholsulfate is counteracted by the presence of the boric acid ester. Forthis reason the skin has a pleasant feeling after washing. The hair issoft, supple and particularly easy to treat.

Example 9 For the preparation of hair wash whereupon the mixture isstirred until cool and perfumed as desired. There is obtained ahair-wash in which the addition of the boric acid ester acts in the samemanner as in the case of the preparation described in the precedingexample.

Example 10 For the preparation of a shaving soap 13.5 kg. stearic acid4.5 kg. sorbitan-monostearate-polyglycol ether and 2.5 kg. petrolatumoil are stirred with each other at 90 C. At this temperature, there areintroduced 4.5 kg. sorbitol 1.0 kg. borax 2.0 kg. t-riethanolamine It isallowed to cool to 40 C. while stirring, whereupon there are slowlyadded id 4 kg. of the molten boric acid-coconut fatty acid ethanolamideester described in Examples 7 to 9.

After the mixture has cooled while stirring, there are added 0.5 kg.perfume and 58.5 kg. water Example 11 The boric acid esters as used inthe preceding examples may be replaced by the following esters:

(a) Ester prepared from 1 mol of boric acid and 3 mole of lauric acidmonoethanolamide. Melting portion of the ester: 108-109" C.

(b) Ester prepared from 1 mol of boric acid, 1 mol of fatty alcohol(derived from coconut fatty acid) and 2 mols of coconut fatty acidmonoethanolamide. Melting point of the ester: 74-75" C.

(c) Ester of a composition similiar to this described under (b) whereinthe fatty alcohol is derived from tallow fatty acid. Melting point ofthe ester: 74-75" C. This ester is especially suited as addition forbars on basis of synthetic detergents.

We claim:

1. A detergent composition consisting essentially of a surface-activeagent which is a member selected from the group consisting of syntheticorganic anionic and nonionic surface-active agents and from l-l00% byweight, referred to said surface-active agent, of a water-insolubleboric acid ester of a fatty acid alkylol amide having a melting point ofat least 40 C., the fatty acid radical of said fatty acid alkylol amidecontaining between 8 and 30 carbon atoms, the alcohol radical of saidfatty acid alkylol amide containing up to 5 carbon atoms, said boricacid ester of said fatty acid alkylol amide containing from 1 to 3 fattyacid alkylol amide molecules for each atom of boron present, any freehydroxyl groups of said boric acid ester of said fatty acid alkylolamide having been esterified with an alcohol having between 1 and 30carbon atoms.

2. A detergent composition according to claim 1, in which saidwater-insoluble boric acid ester of the fatty acid alkylol amide has amelting point of at least 50 C.

3. A detergent composition according to claim 1, in which a molar ratioof fatty acid alkylol amide to alcohol in said ester is between 1:2 and2: 1.

4. A detergent composition according to claim 1, wherein thesurface-active agent is a synthetic organic anionic surface-active agentselected from the group consisting of fatty acid soaps, sulfatedsurface-active agents, sulfonated surface-active agents, fatty acidderivatives of amino acids, fatty acid derivatives of proteinhydrolysates and mixtures thereof.

5. A detergent composition according to claim 1, wherein the surfaceactive agent is a synthetic organic anionic surface-active agentselected from the group consisting of sulphate esters of natural fattyalcohols, sulphate esters of alcohols which are prepared byhydrogenation of natural and synthetic acids, sulphate esters ofpolyvalent alcohols, sulphated fatty acid monoglycerides, sulphatedfatty acid polyglycol ethers and sulphated fatty alcohol polyglycerineethers.

6. A detergent composition according to claim 1, in bar form.

7. A detergent composition according to claim 1, in

which said boric acid ester of said fatty acid alkylol amide is a boricacid ester of a coconut'fatty acid monoethanol-amide.

' 8. A detergent composition according to claim 1 in which said boricacid ester of said fatty acid alkylol amide is a boric acid ester ofcoconut fatty acid monoethanolamide containing 3 molecules of coconutfatty acid monoethanolamide for each atom of boron present.

9. A detergent composition according to claim 1 in which said boric acidester of said fatty acid alkylol amide is a boric acid ester of lauricacid monoethanolamide containing 3 molecules of lauric acidmonoethanolamide for each atom of boron present.

10. A detergent composition according to claim 1 in which said boricacid ester of said fatty acid alkylol amide is a boric acid ester ofstearic acid monoethanolamide containing 3 molecules of stearic acidmonoethanolamide for each atom of boron present.

11. A detergent composition according to claim 1 wherein said boric acidester of said fatty acid alkylol amide is a boric acid ester containing1 molecule of a fatty alcohol derived from tallow fatty acid and 2molecules of :oconut fatty acid monoethanolamide for each atom of Boronpresent.

12. A detergent composition according to claim 1 vherein said boric acidester of said fatty alkylol amide s a boric acid ester containing 1molecule of a fatty alco- 101 derived fronrcoconut fatty acid and 2molecules of coconut fatty acid monoethanolamide for each atom of boronpresent.

13. The. method of preparing a detergent composition consistingessentially of a surface-active agentwhich is a member selected from thegroup consisting of synthetic organic anionic and non-ionicsurface-active agents and from 1-100% by Weight, referred to saidsurface-active agent, of a water-insoluble boric acid ester of a fattyacid alkylol amide having a melting point of at least 40 C., the fattyacid radical of said fatty acid alkylol amide containing between 8 andcarbon atoms, the alcohol radical of said fatty acid alkylol amidecontaining up to 5 carbon atoms, said boric acid ester of said fattyacid alkylol amide containing from 1 to 3 fatty acid alkylol amidemolecules for each atom of boron present, any free hydroxyl groups insaid boric acid. ester of said fatty alkylol amide having been.esterified with an alcohol having between 30 and carbon atoms, whichcomprises admixing the synthetic organic surface-active agent with saidwater-insoluble boric acid ester of a fatty acid alkylol amide, whilethoroughly agitating said mixture.

References Cited in the file of this patent UNITED STATES PATENTS 252,173,448 Katzmann Sept; 19, 1939 2,216,618 Katz Oct. 1, 1940 2,441,063Gilmann May 4, 1948

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A SURFACE-ACTIVEAGENT WHICH IS A MEMBER SELECTED FROM THE GROUP SONSISTING OF SYNTHETICORGANIC ANIONIC AND NONIONIC SURFACE-ACTIVE AGENTS AND FROM 1-100% BYWEIGHT, REFERRED TO SAID SURFACE-ACTIVE AGENT, OF A WATER-INSOLUBLEBORIC ACID ESTER OF A FATTY ACID ALKYLOL AMIDE HAVING A MELTING POINT OFAT LEAST 40*C.,THE FATTY ACID RADICAL OF SAID FATTY ACID ALKYLOL AMIDECONTAINING BETWEEN 8 AND 30 CARBON ATOMS THE ALCOHOL RADICAL OF SAIDFATTY ACID ALKYLOL AMIDE CONTAINING UP TO 5 CARBON ATOMS SAID BORIC ACIDESTER OF SAID FATTY ACID ALKYLOL AMIDE CONTAINING FROM 1 TO 3 FATTY ACIDALKYLOL AMIDE MOLECULES FOR EACH ATOM OF BORON PRESENT, ANY FREEHYDROXYL GROUPS OF SAID BORIC ACID ESTER OF SAID FATTY ACID ALKYLOLAMIDE HAVING BEEN ESTERIFIED WITH AN ALCOHOL HAVING BETWEEN 1 AND 30CARBON ATOMS.